Reaction products of unsaturated hydrocarbons with P4 S10 and PSX3

ABSTRACT

Unsaturated hydrocarbons such as ethylene, propylene, butylene, pentene, cyclohexene and 1,3-butadiene among others are reacted with P 4  S 10  and PSX 3 , wherein X is selected from the group consisting of Cl and Br, under autogenous pressure at temperatures from about 90° C. to about 250° C. The reaction products obtained are useful as intermediates in preparation of agricultural chemicals; lubricant and polymer additives; mercaptoethyl- and mercaptobutylphosphonic acids; and mercaptobutylphosphinic acids.

This is a continuation of application Ser. No. 252,114, filed Apr. 8,1983, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new compounds which can becharacterized as reaction products of unsaturated hydrocarbons with P₄S₁₀ and PSX₃, wherein X is selected from the group consisting of Cl andBr.

2. The Prior Art

Reactions of ethylene with P₄ S₁₀ and PCl₃ are described in U.S. Pat.No. 3,897,491. The reactions are conducted in an autoclave at elevatedtemperature to produce alkyl phosphorus halides.

In U.S. Pat. No. 3,988,368 a process for preparing phenylphosphonothioicdichloride is described. The process consists of reacting benzene withPSCl₃ in the presence of a catalyst. Suitable catalysts include forexample P₂ S₅ and PCl₃ or AlCl₃ and P₂ S₅. The reaction scheme is asfollows: ##STR1##

The reactions of unsaturated hydrocarbons with P₄ S₁₀ and PSX₃ describedin the present invention are not disclosed in the prior art.

SUMMARY OF THE INVENTION

In accordance with the present invention, reaction products ofunsaturated hydrocarbons with P₄ S₁₀ and PSCl₃ are prepared according tothe generalized reaction scheme:

    R.sub.1 R.sub.2 C═CR.sub.3 R.sub.4 +P.sub.4 S.sub.10 +PSX.sub.3 →Products                                          I

wherein X is selected from the group consisting of Cl and Br and R₁,R₂,R₃ and R₄ can be the same or different and are selected from the groupconsisting of hydrogen, C₁ -C₁₀ alkyl and C₁ -C₁₀ alkylene with theproviso that the unsaturated hydrocarbon reactant

    R.sub.1 R.sub.2 C═CR.sub.3 R.sub.4                     ( 1)

can be a cyclic compound.

The reaction is conducted under autogenous pressure at temperatures fromabout 90° C. to about 250° C.

Products of the reaction are useful as intermediates in preparation ofagricultural chemicals; lubricant and polymer additives; mercaptoethyl-and mercaptobutyl-phosphonic acids; and mercaptobutylphosphinic acids.

DETAILED DESCRIPTION OF THE INVENTION

Exemplary unsaturated hydrocarbons and the corresponding reactionproducts of the present invention include, but are not limited to thefollowing:

    ______________________________________                                        UNSATU-                                                                       RATED HY-                                                                     DROCARBON REACTION PRODUCT                                                    ______________________________________                                        CH.sub.2CH.sub.2                                                                         ##STR2##                                                                      ##STR3##                                                                     where x ≧ 1                                                  CH .sub.2CHCH.sub.3                                                                      ##STR4##                                                           1 OR 2 BUTENE                                                                            ##STR5##                                                           1-pentene                                                                                ##STR6##                                                           cyclohexene                                                                              ##STR7##                                                           1,3-butadiene                                                                            ##STR8##                                                           isoprene                                                                                 ##STR9##                                                           ______________________________________                                    

The method of the present invention comprises contacting an unsaturatedhydrocarbon reactant of the general formula:

    R.sub.1 R.sub.2 C═CR.sub.3 R.sub.4                     ( 1)

wherein R₁ R₂, R₃ and R₄ can be the same or different and are selectedfrom the group consisting of hydrogen, C₁ -C₁₀ alkyl and C₁ -C₁₀alkylene with the proviso that said reactant can be a cyclic compound;with other reactants having the general formulas:

    P.sub.4 S.sub.10 ; and                                     (2)

    PSX.sub.3 and optionally PX.sub.3                          ( 3)

wherein X is selected from the group consisting of Cl and Br.

Reactants utilized in the method of the present invention are generallyemployed in stoichiometric amounts, although an excess of any reactantcan be used if desired. The quantity of undesired side products however,is minimized by the use of approximately stoichiometric amounts ofreactants. No catalyst is used or necessary in the method of the presentinvention.

The method is carried out at elevated temperature and pressure. Thereaction temperature is from about 90° C. to about 250° C. Reactionpressure is autogeneous and is generally from about 2 to about 2 toabout 300 atmosphere.

Reaction times can vary over relatively wide ranges and can easily bedetermined by one skilled in the art. Factors affecting reaction timeinclude reactant concentration, temperature and pressure. Increases intemperature and reactant concentration result in decreased reactiontimes. Dilute reactants require longer reaction times than concentratedreactants. Pressure increases reduce reaction time. Typical reactiontimes are from about 1 to about 24 hours.

The method described above can conveniently be effected by introducingthe individual reactants into any reaction zone that can withstand thereaction pressure and be heated to the reaction temperature. A highpressure autoclave rated up to 5000 psig may be required to withstandthe pressure generated at reaction temperatures.

Without intending to be bound thereby, the theory of the presentinvention is as follows:

There are two basic types of unsaturated hydrocarbons that can be usedas starting materials in accordance with the present invention. One typeis mono-unsaturated containing one ##STR10## bond and the other is1,3-dienes containing two conjugated ##STR11## bonds.

The first member of the mono-unsaturated series, CH₂ ═CH₂ is a specialcase in that all of the hydrogens present are on carbons having doublebonds. This causes variations in the reaction based upon reactionconditions. At high temperatures (from about 200° to about 250° C.) thefollowing reaction procedes in high yields: ##STR12## at lower reactiontemperatures (from about 130° to about 170° C.) a glossy solid is formedas shown in the following example:

    4CH.sub.2 ═CH.sub.2 +P.sub.4 S.sub.10 ♭[C.sub.8 H.sub.16 P.sub.4 S.sub.10 ]                                        (5)

This product cannot be distilled or sumblimed due to the likelyformation of a complex high molecular weight compound which stillcontains the basic P₄ S₁₀ structure. The reaction is fairly specific inthe amount of ethylene that reacts for each P₄ S₁₀ present. When excessethylene is added to the reaction mixture it remains unreacted.

Hydrolysis of the low temperature product with hot water gives thefollowing products per starting P₄ S₁₀ :

HSCH₂ CH₂ SH;

2HSCH₂ CH₂ PO₃ H₂ ;

H₂ O₃ PCH₂ CH₂ PO₃ H₂ ;

6H₂ S; and

some H₃ PO₄.

When the low temperature reaction is conducted in the presence of PSCl₃,the same basic phosphorus acids are found on hydrolysis along with moreH₃ PO₄. Since H₂ O₃ PCH₂ CH₂ PO₃ H₂ is found, there is an indicationthat some ethylenes reacted to form a PCH₂ CH₂ P intermediate.

Mono-unsaturated hydrocarbons above ethylene react differently. Forexample, propylene which has three allylic hydrogens yields followingpossible intermediate ##STR13## This reaction appears to take place attemperatures of about 100° C. The next step of the reaction is theaddition of the SH to a double bond. For all compounds except thepropylene this then results in the formation of a cyclic compound. Inthe case of propylene, however, the following intermediate is formed:##STR14## When PSCl₃ is present in the reaction with propylene the aboveintermediates (6) and (7) give the following products in low yield:##STR15##

There are various possible reasons why a cyclic compound is not formedreadily from the compound of equation (6). For example, a 4-memberedring having the equation ##STR16## would be strained and therefore notreadily formed.

With 1-butene, a cyclic product is formed from an intermediate asfollows: ##STR17##

The 1,3-dienes appear to react according to the present invention undera new Diels-Alder mechanism in which P═S of the P₄ S₁₀ acts as thedienophile to which a 1,3-diene undergoes a 1,4 cycloaddition. Thisproduces a product having the formula: ##STR18##

Several conjugated dienes can be used as starting materials pursuant tothe present invention. A general equation for these materials is asfollows: ##STR19## where R₁, R₂, R₃, R₄, R₅ and R₆ can be the same ordifferent and are selected from the group consisting of H; saturated andaromatic hydrocarbons; ##STR20## Cl; F; --C.tbd.N; oxygen and sulfurcontaining ethers and esters; tertiary amines; and groups such as PR;Si(OR)_(x) ; S(O)(OR)_(x) (R)_(y) and B(R)_(x) where R is a hydrocarbonand x and y are intergers.

Hydrolysis of the various reaction products of the present invention cangive numerous acids. The following are examples: ##STR21##

Products of the reaction can be purified by vacuum distillation andother conventional methods such as extraction, sublimation andcrystallization.

Identification of products can be achieved by infrared spectra, ¹ Hnuclear magnetic resonance spectra, ³¹ P nuclear magnetic resonancespectra, boiling point analysis and elemental analysis.

Typical yields of the method of the present invention are from about 10%to about 90% based upon phosphorus reacted.

The products of the present invention are useful as intermediates inpreparation of agricultural chemicals; lubricant and polymer additives;mercaptoethyl and butylphosphonic acids; and mercaptobutylphosphinicacids. For example, a cyclic acid chloride produced in accordance withthe present invention can be reacted with an alcohol in the presence ofan amine to form lubricant and polymer additives as follows: ##STR22##

The present invention will be more fully illustrated in the Exampleswhich follow.

EXAMPLE I

In a 300 ml 316 stainless steel autoclave were placed 28 g 1-butene (0.5moles), 28 g PSCl₃ (0.1666 mole) and 36.9 g P₄ S₁₀ (0.0833 mole). Theautoclave was heated at 200° C. for 18 hours. The crude yield of productwas 86 g. The product was isolated by distillation having a boilingpoint of 82° C. at 0.01 mm Hg pressure. The yield of product was 58.4 gor 63% theory.

Analysis: calculated for C₄ H₈ ClPS₂ : 19.0 Cl; 16.6 P; 34.3 S. Found:19.5 Cl; 16.4 P; 34.8 S.

n_(D) ²⁵ : 1.6133. ³¹ P-nmrδdoublet 117.4, 118.1 ppm (two isomerspresent due to different CH₃ positions).

Hydrolysis of ##STR23## was then conducted to give ##STR24## as follows.

A 92.9 g sample of product was hydrolyzed in 500 ml of refluxing 20% HClfor 2 days. The solvent was evaporated to yield 80.3 g white solidproduct having a 95% yield. A sample was crystallized from etherheptane.Melting point was 142°-143° C.

Analysis: calculated for C₄ H₁₁ O₃ PS: 28.24 C; 6.47 H; 18.2 P; 18.8 S.Found: 28.0 C; 6.4 H; 18.1 P; 19.15 S.

The product was titrated with aqueous NaOH which showed a dibasic acidof MW 170. Theory for ##STR25##

³¹ P-nmrδ=30.7 ppm

    ______________________________________                                        .sup.13 C--nmr δ (ppm)                                                                  J(Hz)                                                         ______________________________________                                        36.8            18                                                            34.4             4                                                            25.5            135                                                           24.4             0                                                            ______________________________________                                    

One sulfur was then removed as follows: ##STR26## 37.3 g C₄ H₈ ClPS₂(0.2 moles) and 54.2 g φ₃ P (0.2 mole) were placed in a 250 mldistillation flask. The mixture was heated to 80° C. This was followedby solidification of the reactants due to formation of φ₃ PS. Theproduct was distilled under 0.1 mm Hg pressure to give 28.5 g or 92.2%yield.

n_(D) ²⁵ =1.5790.

³¹ P-nmr=doublet 168.7 and 163.3 ppm

Hydrolysis of this product in aqueous HCl yielded. ##STR27## based onH-nmr, ^(d) 31 P-nmr and ¹³ C-nmr spectra. ³¹ P-nmrδ=128.1 ppm.

Repeating the above process using cis-2-butene instead of 1-butene thedistilled yield of product was 55.5 g or 59.5% yield. It had the samen_(D) ²⁵ and ³¹ P-nmr spectra as the above product.

Again repeating the first process above, using trans-2-butene instead of1-butene the distilled yield of product was 56.2 g or 60.3% theory.

It had the same n_(D) ²⁵ and ³¹ P-nmr spectra as the other products.

EXAMPLES II

In a 300 ml 316 stainless steel autoclave were placed 52.5 g 1-pentene(0.75 mole), 42.25 g PSCl₃ (0.25 mole) and 55.5 g P₄ S₁₀ (0.125 mole).The autoclave was heated at 200° C. for 18 hours. The crude yield was142 g. The crude product was distilled to give 90 g material having aboiling point range of 111°-160° C. at 0.5 mm Hg pressure. Analysis by³¹ P-nmr indicate 5 different phosphorus compounds were present. Thismaterial was redistilled at 0.1 mm Hg pressure and 9 different fractionstaken have a boiling range of 91° to 97° C. Fraction number 8 (9.2 g)assayed 72% cyclic product based on ³¹ P-nmr (δ=close doublet at 115.9ppm) n_(D) ²⁵ =1.6006.

EXAMPLE III

In a 300 ml 316 stainless steel autoclave were placed 61.5 g cyclohexane(0.75 mole), 42.25 g PSCl₃ 0.25 mole) and 44.4 g P₄ S₁₀ (0.1 mole). Theautoclave was heated at 200° C. for 12 hours. The crude yield was 137 g.The product was distilled at 0.05 mm Hg pressure to give 47 g ofmaterial having a boiling point of 135°-140° C. Yield=34%. This materialcrystallized on cooling. It had a melting point of 73°-76° C. It wascrystallized from hot heptane to give material having melting point of75°-77° C.

Analysis: calculated for C₆ H₁₀ ClPS₂ : 16.7 Cl; 14.6 P; 29.2 S. Found:16.6 Cl; 13.4 P; 29.7 S.

³¹ P-nmrδ=122.8 ppm.

    ______________________________________                                        Found:    .sup.13 C--nmr                                                                         δ (ppm)                                                                              J(Hz)                                         ______________________________________                                                     19.1       singlet                                                            28.2       singlet                                                            33.5       singlet                                                            39.1       doublet (11)                                                       52.2       doublet (50)                                                       56.5       doublet (3)                                           ______________________________________                                    

Using the same reaction conditions, several runs were made in which thereactant ratios were changed. The results are listed below.

    ______________________________________                                        Cyclohexene Reaction Study                                                    Reactant Molar Ratio                                                          cy-C.sub.6 H.sub.10 :                                                                   PSCl.sub.3 : P.sub.4 S.sub.10 :                                                                    % Yield                                        ______________________________________                                        1         0.333        0.1333  34                                             1.2       0.333        0.1333  25                                             1         0.4          0.1333  24                                             1         0.333        0.16    38                                             ______________________________________                                    

EXAMPLE IV

In a 300 ml 316 stainless steel autoclave were placed 74 g P₄ S₁₀(0.1667 mole); 56.3 g PSCl₃ (0.34 mole) and 42 g propylene (1 mole). Theautoclave was heated at 240° C. for 8 hours. The crude product wasdistilled to give ##STR28## having a boiling point of 66° C. at 0.01mmHg pressure.

Analysis: calculated for C₃ H₆ ClPS₂ : 20.5 Cl; 17.9 P; 37.1 S. Found:20.6 Cl; 17.4 P; 36.0 S.

n_(D) ²⁵ =1.6367.

³¹ P-nmrδ=118 ppm.

EXAMPLE V

In a 300 ml 316 stainless steel autoclave were placed 33.3 g P₄ S₁₀(0.075 mole);101.7 g PSCl₃ (0.6 mole); 27.5 g PCl₃ (0.2 mole) and 25.2 gpropylene (0.6 mole). The autoclave was heated at 125° C. for 12 hoursfollowed by cooling. After cooling, a light tan liquid weighing 183 gwas poured out. The product was distilled at 20 mmHg to give 50.3 gunreacted PCl₃ and PSCl₃ and was then distilled at 0.01 mmHg to give41.5 g (CH₃)₂ CHSPSCl₂ and 58.2 g crude ##STR29## having a boiling pointat 0.1 mmHg of 130°-140° C.

On cooling, the latter fraction formed a crystalline solid which wasremoved by filtration. The yield of crystalline solid was 20 grams.Melting point was 58°-60° C.

Analysis: calculated for C₃ H₄ Cl₄ P₂ S₂ : 46.1 Cl; 20.1 P; 20.8 S.Found: 45.7 Cl; 20.0 P; 21.0 S.

EXAMPLE VI

In a 300 ml 316 stainless steel autoclave were placed 22.2 g P₄ S₁₀(0.05 mole); 67.8 g PSCl₃ (0.4 mole); 27.5 g PCl₃ (0.2 mole) and 25.2 gpropylene (0.6 mole). The autoclave was heated at 130° C. for 12 hours.The crude yield was 122 grams. ³¹ P-nmr of the crude product gave thefollowing results:

    ______________________________________                                        MATERIAL            δ  AREA %                                           ______________________________________                                        PCl.sub.3                 219    49                                            ##STR30##                 97    1.7                                          CH.sub.2CHCH.sub.2 PSCl.sub.2                                                                            85    16                                           Unkown                     78    1                                                                       74    5                                            Cl.sub.2 (S)PCHCHCH.sub.2 PSCl.sub.2                                                                     65                                                 (CH.sub.3).sub.2 CHSPSCl.sub.2                                                                           70    19                                           PSCl.sub.3                 32    8                                            ______________________________________                                    

Distillation at 3 mmHg gave 6.7 g of CH₂ ═CH-CH₂ PSCl₂ having a boilingpoint of 33°-35° C.; n_(D) ²⁰ 1.5516.

EXAMPLE VII

Reactions using 1,3-butadiene were run under various reaction conditionsusing different reactant ratios. The effect of using a solvent to dilutethe reaction and reduce the dimerization of 1,3-butadiene also wasdetermined.

All reactions shown in Table I were run in a 300 ml 316 stainless steelautoclave on a 0.5 mole scale of 1,3-butadiene. All reactions were runfor 10 hours. Fifty grams of toluene was added when it was used as asolvent. The reaction conditions and results are shown below. Theproduct was isolated by distillation at 0.1 mm Hg pressure. The producthas a boiling point of 109°-110° C. at this pressure. It forms a solidon cooling and can be crystallized from hot heptane. Meltingpoint=63°-66° C.

                  TABLE I                                                         ______________________________________                                        TEMP.  REACTANT MOLE RATIO                                                                              Solvent                                             °C.                                                                           C.sub.4 H.sub.8 :                                                                      PSCl.sub.3 :                                                                           P.sub.4 S.sub.10                                                                     (toluene)                                                                            % Yield                                ______________________________________                                        130    1        0.333    0.1667 no     36                                     150    1        0.333    0.1667 yes    50                                     150    1        0.5      0.1667 yes    54                                     150    1        2        0      no      0                                     180    1        0.5      0.1667 no     14                                     150    1.2      0.5      0.1667 yes    69                                     150    1.2      0.333    0.1667 yes    69                                     150    1.2      0.333    0.1333 yes    71                                     ______________________________________                                    

³¹ P-nmr=78.5 ppm

H-nmr=vinyl to paraffin H ratio=1:2

¹³ C-nmr=(P--C) 44.3 ppm, J=63 Hz; (P--S--C) 33.2 ppm, J=4.0 Hz; (C═C)124.0 ppm, (complex vinyl).

Analysis: calculated for C₄ H₅ ClPS₂ : 19.2 Cl; 16.8 P; 34.68 S. Found:19.9 Cl; 16.8 P; 34.4 S.

EXAMPLE VIII

In a 300 ml 316 stainless steel autoclave were placed 29.6 g P₄ S₁₀(0.667 mole); 37.7 g PSCl₃ (0.222 mole); 22.9 g PCl₃ (0.1667 mole); 34 gisoprene (0.5 mole) and 50 g toluene as a diluent. The autoclave washeated at 115° C. for 12 hours. Crude yield was 170 g. The product wasisolated by distillation after 106 g of low boilers were removed. Yieldwas 50 g with a boiling point of 105°-130° C. at 0.01 mmHg.

³¹ P-nmr analysis indicated that the product consisted ##STR31## and 10%unknown.

Crystallization from heptane gave pure ##STR32## having a melting pointof 56°-58° C.

Analysis: calculated for C₅ H₈ ClPS₂ : 17.9 Cl; 15.6 P; 32.2 S. Found:18.1 Cl; 15.6 P; 32.3 S.

³¹ P-nmrδ=83 ppm

    ______________________________________                                        .sup.13 C--nmr δ (ppm)                                                                 J(Hz)                                                          ______________________________________                                        27.5           doublet (14)                                                   33.1           doublet (6)                                                    48.8           doublet (61)                                                   119.2          doublet (15)                                                   133.3          doublet (10)                                                   ______________________________________                                    

Having set forth the general nature and some examples of the presentinvention, the scope is now particularly set forth in the appendedclaims.

What is claimed is:
 1. A composition selected from the group consistingof: ##STR33## and isomers thereof, wherein X is selected from the groupconsisting of Cl and Br.
 2. The composition of claim 1 of the formula:##STR34## wherein X is selected from the group consisting of Cl and Br.3. The composition of claim 1 of the formula: ##STR35## wherein X isselected from the group consisting of Cl and Br.
 4. The composition ofclaim 1 of the formula: ##STR36## and isomers, wherein X is selectedfrom the group consisting of Cl and Br.
 5. The composition of claim 1 ofthe formula: ##STR37## wherein X is selected from the group consistingof Cl and Br.
 6. The composition of claim 1 of the formula: ##STR38##wherein X is selected from the group consisting of Cl and Br.
 7. Thecomposition of claim 1 of the formula: ##STR39## and isomers, wherein Xis selected from the group consisting of Cl and Br.
 8. A compositionselected from the group consisting of:

    X.sub.2 P(S)CH.sub.2 --CH═CH--P(S)X.sub.2 and

    (OH).sub.2 P(O)CH.sub.2 --CH═CH+13 P(O)(OH).sub.2

and isomers thereof, wherein X is selected from the group consisting ofCl and Br.
 9. The composition of claim 8 of the formula: ##STR40##wherein X is selected from the group consisting of Cl and Br.
 10. Thecomposition of claim 8 of the formula: ##STR41##
 11. A compositionselected from the group consisting of: ##STR42## and isomers thereof.12. The composition of claim 11 of the formula: ##STR43##
 13. Thecomposition of claim 11 of the formula: ##STR44##
 14. The composition ofclaim 11 of the formula: ##STR45##
 15. A method of preparing reactionproducts of unsaturated hydrocarbons, P₄ S₁₀ and PSX₃ wherein X isselected from the group consisting of Cl and Br comprising contacting anunsaturated hydrocarbon reactant of the general formula:

    R.sub.1 R.sub.2 C═CR.sub.3 R.sub.4                     I

wherein R₁, R₂, R₃ and R₄ can be the same or different and are selectedfrom the group consisting of hydrogen, C₁ -C₁₀ alkyl and C₁ -C₁₀alkylene with the proviso that said reactant can be cyclic; and with thefurther proviso that said reactant is not ethylene; with reactantshaving the general formulas:

    P.sub.4 S.sub.10 ; and                                     II

    PSX.sub.3                                                  III

wherein X is as defined above, at a temperature from about 90° C. toabout 250° C. and under autogenous pressure.
 16. The method of claim 1wherein the unsaturated hydrocarbon reactant is selected from the groupconsisting of propylene, 1-butene, 2-butene, 1-pentene, cyclohexane, 1,3butadiene and isoprene.
 17. The method of claim 1 wherein the reactionproducts are selected from the group consisting of: ##STR46## wherein Xis selected from the group consisting of Cl and Br.